Treatment of carroted fur fibers



Patented June 5, 1951 UNITED STATES PATENT OFFICE TREATMENT OF CARROTED FUR FIBERS No Drawing. Application May 8, 1948, Serial No. 25,995

6 Claims.

- l 1 This invention relates to carroted fur fibers and more particularly to a novel treatment thereof effecting improved felting qualities and other desirable results. It is Well known in the art to process rabbit, hare, and similar types of fur by any of a variety of carroting solutions,

whereby felting properties are imparted to the fur; and to employ such carroted fur in the manufacture of hats. In making hats, the carroted fur is subjected to a series of wet-processing operations for forming the fibers into a felt and shrinking the felt to size, during which operations the fur is treated with water at temperatures ranging from 150 to 212 F. Thereby there are produced unfinished hat bodies which are subsequently subjected to a series of dryprocess operations for converting them into finished hats.

Briefiy summarizing the usual practice, the

fur, after being carroted on the skins, is dried, and then cut from the skins. The cut carroted fur, after piece dropping, to remove larger pieces of pelt and attached fur which may be included in the fur leaving the cuttin machine, is then subjected to one or more blowing operations to remove any material heavier than the fur.

At the hat factory, the fur which is processed may be 100 per cent carroted fur (long stock) or carroted fur mixed with fillers (short stock) consisting of raw fur, boiled fur, roundings and/or other non-fur substances of fibrous nature. In either event, the fur is customarily subjected to a series of wet-processing operations toform felt and shrink the latter into hat bodies. These operations usually include: (1) Forming, in which the fur is suspended in air and. sucked on to a revolving cone. The layer-of fur on the con is covered with wet bur-' lap, held in place by suitable retaining means such as a perforated cone-shaped metal guard.

(2) Wet-out, in which the cone assembly, including the fur layer, issubmerged in water for 30 seconds at temperatures in the neighborhood of 150 F. Sometimes the forming and wet-out steps are carried out concurrently by spraying water on to the fur layer on the forming cone.

(3) Hardening, in which the cone of fur, hardly more than a cobweb, is stripped from the forming cone, and then worked in wet flannel cloths to shrink and harden it enough'to withstand the handling of the next operation.

(4) Starting, in which the wet body from the hardening operation, stacked and wrappedin a bundle with other similar Wet bodies, is tumbled on corrugated rolls. During this starting" operation the wet bodies are handled at intervals by an operator to insure desired shrinkage in different directions.

(5) Sizing, in which the bodies are worked at different pressures and temperatures, while being repeatedly drenched with hot water, on machines comprising rolls and belts, either of which may be grooved or corrugated. The bodies are thereby shrunk to approximately their full limit of shrinkage.

(6) Dyeing, in which the bodies are immersed in a hot dye-bath for a period suflicient to insure the desired coloring effect. This may take place during the sizing operation, or between different stages thereof.

After further wet-processing treatments, in-' cluding stretching and blocking, the sized hat bodies are passed on to the front shop department of the factory wherein they are subjected to a series of dry processing operations convert ing them into finished hats.

It will thus be seen that in hat manufacture the fur fibers undergo a series of felting and shrinking operations involving treatment "with hot water at temperatures generally ranging from to 212 F. In addition the fibers are subjected to mechanical working.

These conditions lead to annoying weakening and breakage of fibers. In addition, undesirable losses of fiber weight occur in the wet processing operations, due particularly to solution of degraded protein materials resultingfrom carroting, ranging from acid meta proteins and proteoses to the very soluble amino acids.

The present invention provides a novel mode of treatment of the carroted fur fibers which diminishes their susceptibility to breakage, and also reduces the solubility losses encountered in the wet-processing steps. It furthermore improves their feltability and the quality of the resulting felt.

The invention further comprises a new carroted fur product resulting from our novel treatment and presenting the advantages above noted, in addition to others hereinafter pointed out.

We have found that the foregoing advantageous results may be obtained effectively and expeditiously by treating carroted fur fibers with solutions containing protein-reactive or anic compounds, various examples of which will be presently set forth.

The invention also comprises further features which will be hereinafter described and claimed.

In treating the carroted fur we prefer that the fur be cut from the pelt after carroting, to

immersion of the cut carroted fur in the treating solution to insure desirable uniformity of application.

No special care in preparation of the cut fur is required. The cut fur may be used:

(1) direct from the cutting machine; or

(2) after piece-dropping (clearing) of the out fur, which removes the larger pieces of pelt and attached fur; or

(3) after one or more blowing operations which remove smaller pieces, dags, hair, or any substance heavier than fur.

Out for which has been subjected to the clearing operation is preferred, because it is sufi'i ciently cleared of pelt pieces, and the subsequentlyproce'ssedfur can be subjected to one or more-blowing operations to separate any dirt or debris, as noted hereinafter. The carroted cut fur as it comes from the clearing or any subsequent blowing operation is in excellent physical condition for the chemical treatment.

In applying the process to the carroted cut fur, the major requirement is a uniform application'of-the'sol-ution under conditions which will not induce felting. Any felting will cause the fur to form wads or "balls which are impossible to be again separated "into individual fibers. Such felting, therefore, constitutes a complete loss of such wads, balls,'or nibs, which must be removed from the processed fur. Furthermore the severe operations required to tear the wads from the processed fur would cause damage to the latter.

A'siinp'le method of processing is exemplified by' that which has been frequently used in our Work, and inv which the fur is maintained sufiiciently quiescent to avoid felting.

(:1) Ihe carroted fur is packed in a-suitable container with a preforated false bottom. The

unit hasxa multiplici-ty of holes about 5 inch in diameter inthe false bottom which makes it unnecessary to -use any filter cloth or other lining. The solution of chemicals is pumped in, either from the bottom or at the top, the amount being suifi'cien't to completely'submerge the fur. t is customary to use a perforated'cover on top of the fur as a further protection against movement. This cover may be rigid or it may be a piece of burlap or other flexible material.

(2) The solution is then recirculated to assume uniformity of processing. This is desirable because there may be a decrease in concentration of the solution as reactive chemicals are used up locall-y. The'ti-m'e, temperature, concentrationsand oth'erconditions depend to some extent on tliesize of the batch'of fur. Satisfactory operation with 0.5 lb. batches has been achieved in 20-to 30,-minutesat -180 to -200-F. with 0.05 to .22 per cent aqueous solutions of a number of reagents-examples of which will be presently specified. It is obvious that suflicient amount of solution or'sufficient concentration must be used to guarantee an adequateamount of reactive-chemical.

"Other satisfactory operation has been attained at temperatures as lowas 100 F. but for longer times. The higher temperature of operation is preferred and is, of course, much more practical. As an'example, a larger scale (300 lb.) treatment in the course of our operations was run at 160 F. for 1.5 hours.

At completion of the run, the spent or partly spent solution is drained off and the fur is adequately rinsed with water, very dilute acid, or other rinsing solution. Present practice with most reagents has been to rinse three times with water at about F. However, acid rinse at 'pH about 3 has been desirable with certain reagents, particularly when the treatment has been at pH 5 or higher, i. e., above the isoelectric point of uncarroted fur.

(3) The excess water is removed by any suitable means, such as by centrifuge or squeeze rolls. The moist product can be air dried slowly or preferably oven-dried at an accelerated rate. Trials have been made up to 220 F. without noticeable difference in the felting properties or quality of the product.

(4) The dried processed fur is loose and free from felted masses. It will normally be subjected to additional mechanical operations which further loosen and fluff it and mix it to further eliminate any non-uniformity. The final step is blowing, which separates any dirt or debris, particularly that which was part of the untreated product. These mechanical standard procedures in fur processing and they need no modification to adapt them to the handling of the product. 1

Instead 'of treating the fur in batches as described above, the operation may be made continuous. This may be accomplished by holding the fur between suitable belts, which may be of thin open weave cloth, and passing this submerged sandwich through the treating solutions. If desirable, the fur may be brought up, squeezed, and re-immersed one or more times-and then finally passed through squeeze rolls and on into the rinsing operations. These may conveniently be of the-same'type as the main processing operations. Drying can then be done by passage through a continuous type of oven.

The above described methods of subjecting the carroted fur to a treating solution may be employed for applying to the fur protein-reactive organic compounds, whether cationic anionic, or non-ionic. We prefer cationic protein-reactive organic compounds because-of the excellent-results obtained thereby, and further, because we have found that they not only do not impair the dyeing of the fur but that they in fact materially improve its dyeing properties. At the same-time, in the course of our investigations, we have found various anionic and non-ionic protein-reactive organiccompounds which-may be applied to the fur in the same manner asaboveset forth, and which, when so applied, effect beneflcial results in improving the quality and feltability of the fur and in reducing solubility losses.

Wefindjthat variations in pH haveonly slight, if any, influence upon the results obtained with non-ionic -.protein-reactive organic compounds. However, control of pH during treatment enables different results-to be obtained with either anionic or cationic protein-reactive organic compounds. The usualpH of carroted fur varies approximate: ly fromaround 3 to 4.

The anionic protein-reactive reagents react well in the range near pH 3 and many are sub stantive up to an actual weight gain of l0-or more percent of the weight of the fur. This gain is decreased by increase in pH up to around 4.5 to 5.0. a

Cationic protein-reactive reagents give small weight increases or slight actual losses in the range near pH 3. Substantial weight .gains may operations are 7 be induced at. pH 4 or above. Sinceimproveinent in felting, including quality of product, lowered processing losses, and enhanced" dyeing, have been the main objective, these Weight gains have not been evaluated other than as an additional advantage. 1

It is desirable that the pH of the treating solution containing the protein reactive-agent (whether anionic, cationic, or non-ionic) should not exceed '7.

The concentrations of the protein-reactive agents may be varied substantially, depending uponthe results desired. We have obtained good results with aqueous solutions of said reagents in concentrations varying from .05% to 1%.

The processing may be carried out on partly formed felt instead of loose fur. This could be done in the manner above described for the treatment of loose fur. It may also be done as part of the ffwet-out, hardening, starting, and sizing stages, by including the protein-reactive organic compounds in the water or solutions employed in these wet-processing steps. This is not considered as desirable as the treatment of loose fur, because the control of processing losses is lost in those stages which precede the treatment.

Among the water soluble cationic protein-reactive organic compounds which'may be utilized in the processes of this invention for the production of; the improved carroted fur fibers are cationic protein-reactive organic quaternary salts havingat least carbon atoms, such as or anic quaternary halides having at least 10 carbon atoms, and acid salts of nitrogenous organic compounds having at least 10 carbon atoms, such as salts of tertiary amines having at least 10 carbon atoms.

The cationic protein-reactive organic quaternary salts having at least 10 carbon atoms have the following formula:

in which R is an alkyl, aryl, aralkyl, hydrocarbon polyether radical, or a carboxyalkylene radical, and R1, R2 and R3 are alkyl, aryl or aralkyl radicals or a residue which forms with the nitrogen of the formula a heterocyclic organic compound, and X is a suitable acid residue, such in which R1, R2 and R3 are hydrogen, alkyl, aryl, aralkyl, acyl or carboxyalkylene radicals or the residue which forms with the nitrogen of the formula a heterocyclic organic compound, and X is a suitable acid residue, such as a halogen. If the acid salt is not a heterocyclic compound, then at least one of the members R1, R2 and R3 is an alkyl, aryl, aralkyl, acyl or carboxyalkylene group.

Examples of protein-reactive quaternary ammonium salts are: alkyl dimethyl benzyl ammonium halides, such as lauryl dimethyl benzyl ammonium chloride, cetyl dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium bromide and trimethyl benzyl ammonium chloride; lauryl pyridinium chloride; alkyl isoquinolinium chlorides; polyalkyl naphthalene methyl pyridinium chlorides; alkyl trimethyl ammonium halides, such as lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide and stearyl trimethyl am-. monium chloride; octylphenoxyethoxyethyldimethyl benzyl ammonium chloride;.and otcyl creosoxyethoxyethyldimethyl benzyl ammonium chloride.

Other quaternary ammonium salts which are satisfactory are those containing one or more pentachlorophenate groups.

Examples of protein-reactive acid salts of nitrogenous organic compounds are the reaction products of the acylation of the primary or secondary amino groups of a -alkyl-N-amino alkyl imidazoline, such as described in U. S. Patent 2,200,815 (May 14, 1940).

In addition to the organic quaternary salts and acid salts of nitrogenous organic compounds, certain amine esters and organic free bases are effective cationic protein-reactive organic compounds. Examples of such compounds are the reaction products of alkanolamines with fatty acids, such as the reaction product of amino ethyl ethanolamine and oleic acid, as described in U. S. Patent No. 2,267,965 (Dec. 30, 1941);:

- amine esters of long chain fatty acids; and aminesalts of fatty acid amides.

Examples of anionic protein-reactive organic: compounds are dialkyl esters of sodium sulfosuccinic acid, such as the dioctyl ester of sodium sulfosuccinic acid, the diamyl ester of sodium sulfosuccinic acid and the diisobutyl ester of sodium sulfosuccinic acid, alkyl aryl sodium sulfonates, such as isoropyl naphthalene sodium sulfonate and esters of the sodium sulfonate salts of fatty acids. These compounds give positive weight changes during treatment in the usual manner. Reactivity is greater at pH values below 4 and decreases with the elevation of pH, giving almost no change at pH 6.

Polyalkyl ether condensates of fatty acids are examples of non-ionic protein-reactive materials.

The terms and expressions which we have employed are used in terms of description and not of limitation, and we have no intention, in the use of such terms and expressions, of excluding any equivalents of the features desecribed or portions thereof, but recognize that various modifications are possible within the scope of the invention claimed.

We claim:

1. In the treatment of carroted fur T0! the production of fur felt, the step of applying to the carroted fur an aqueous solution containing at least 0.05% of a cationic protein-reactive organic compound having at least ten carbon atoms.

2. In the treatment of carroted fur for the production of fur felt, the step of applying to the carroted fur an aqueous solution containing at least 0.05% of a cationic nitrogenous proteinreactive organic compound having at least ten carbon atoms. I

3. In the treatment of carroted fur for the production of fur felt, the step of applying to the carroted fur an aqueous solution containing at least 0.05% of a cationic protein-reactive quaternary ammonium salt having at least carbon atoms.

4. In the treatment of carroted fur for the production of fur felt, the step of applying to the carroted fur an aqueous solution containing at least 0.05% of a cationic protein-reactive ter tiary amine salt having at least 10 carbon atoms.

5. Inthe production of fur for the manufacture of fur felt, the steps of applying to a mass of cut carroted fur, an aqueous solution containing at least 0.05% of a cationic protein-reactive or'ganiccompou-nd having at least ten carbon atoms while maintaining said fur sufficiently quiescent to prevent felting during said application of said compound.

" 6. In the production of fur for the manufacture offur felt, the step of applying to carroted fur onthe pelt an aqueous solution containing at least 0.05% of a cationic protein-reactive organic compound having at least ten carbon atoms.

. ADELBERT VJ. HARVEY.

DWIGHT L. DEARDORFF.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,802,258 'Jaeck' Apr. 21, 1931 2,087,855 Fabian July 30, 1937 2,325,236 Fabian -i July 27, 1943 FOREIGN PATENTS Number Country Date 381,418 Germany Oct. I, 1923 

1. IN THE TREATMENT OF CARROTED FUR FOR THE PRODUCTION OF FUR FELT, THE STEP OF APPLYING TO THE CARROTED FUR AN AQUEOUS SOLUTION CONTAINING AT LEAST 0.05% OF A CATIONIC PROTEIN-REACTIVE ORGANIC COMPOUND HAVING AT LEAST TEN CARBON ATOMS. 